Wetting agents for concrete compositions

ABSTRACT

The present invention relates to a concrete-forming composition comprising: 
     (a) a base component consisting of a combination of cement and silica, 
     (b) water, as a carrier, and 
     (c) from about 0.01% to about 25% by weight based on the weight of the composition of a wetting agent selected from the group consisting of piperazine-substituted organosulfonates, piperazinone-substituted organosulfonates, and combinations thereof, and optionally 
     (d) a polycarboxylated alcohol alkoxylate.

This application is a division of application Ser. No. 08/324,954, filedon Oct. 18, 1994, which is a continuation-in-part of application Ser.No. 08/189,369, filed on Jan. 31, 1994, now U.S. Pat. No. 5,360,457.

FIELD OF THE INVENTION

The present invention relates generally to adhesive compositions andcleaning compositions, and more specifically, to a wettingagent/surfactant that enhances the cleaning efficacy of metal andconcrete cleaning compositions and the adhesion efficacy of adhesivecompositions.

BACKGROUND OF THE INVENTION

Piperazine salts, such as the aminoethylpiperazine salt of diphenylether disulfonic acid, are known in the prior art. For example, U.S.Pat. No. 5,262,535 discloses that these salts are useful as cleaningagents for such articles as plastics and vinyl. Likewise, certain2-piperazinones (which contain keto-substitution on the ring) aredisclosed in compositions containing an alkali metal, alkaline earthmetal, or ammonium salt of alkylated diphenyl oxide sulfonate as asurfactant, alone or in combination with a nonionic surfactant that maycontain a mixture of ethoxylated and propoxylated alcohol, as taught inU.S. Pat. No. 5,196,146. The '146 patent teaches that the compositionsdisclosed therein are useful in cleaning grease and oil from metal,plastic, glass, and other surfaces. However, the present inventors havefound that the 2-piperazinones disclosed in the '146 patent do notreact, in accordance with the preparation process of that patent, withthe diphenyl oxide sulfonate surfactant disclosed therein to provide thecorresponding piperazinone salt of diphenyl ether disulfonic acid.

There is an need in the marketplace for additives that are useful inenhancing the bonding efficacy of adhesives, and in improving thecleaning efficacy of hard surface cleaners, such as concrete cleaners.The present invention provides one solution to these needs.

SUMMARY OF THE INVENTION

In one aspect, the present invention relates to a concrete-formingcomposition comprising:

(a) a base component consisting of a combination of cement and silica(e.g., sand),

(b) water, as a carrier, and

(c) a wetting agent, in an amount of between about 0.01% and about 25%by weight based upon the weight of the composition, selected from thegroup consisting of piperazine-substituted organosulfonates,piperazinone-substituted organosulfonates, and combinations thereof.

In another aspect, the present invention relates to an adhesive or paintcomposition comprising:

(a) a base polymer selected from the group consisting of acrylic resins,methacrylic resins, alkyd resins, styrene-butadiene resins, latexresins, and combinations thereof,

(b) a wetting/leveling agent selected from the group consisting ofpiperazine-substituted organosulfonates, piperazinone-substitutedorganosulfonates, and combinations thereof, and

(c) a surfactant selected from the group consisting of alcoholalkoxylates, organic and inorganic salts of polycarboxylated alcoholalkoxylates, and combinations thereof, wherein the amount of component(a) is between about 20 and about 75 weight percent, the amount ofcomponent (b) is between about 0.01 and about 25 (advantageously betweenabout 0,015 and about 10) weight percent, and the amount of component(c) is between about 10 and about 75 weight percent, all weight percentsbeing based upon the total weight of said adhesive or paint composition.

In another aspect, the present invention relates to a cleaningcomposition comprising:

(a) at least one additive selected from the group consisting ofdetergents, corrosion inhibitors, organic and aqueous carriers, andcombinations thereof,

(b) a wetting/cleaning agent selected from the group consisting ofpiperazine-substituted organosulfonates, piperazinone-substitutedorganosulfonates, and combinations thereof, and

(c) a surfactant selected from the group consisting of alcoholalkoxylates, organic and inorganic salts of polycarboxylated alcoholalkoxylates, and combinations thereof, wherein the amount of component(a) is between about 20 and about 95 weight percent, the amount ofcomponent (b) is between about 0.01 and about 25 (advantageously betweenabout 0.015 and about 10) weight percent, and the amount of component(c) is between about 10 and about 75 weight percent, all weight percentsbeing based upon the total weight of said cleaning composition.

In yet another aspect, the present invention relates to a method ofenhancing the bonding efficacy to a porous substrate of an adhesive orpaint composition comprising a polymer or polymerizable monomer whichcomprises admixing with said composition, prior to curing saidcomposition on said substrate, a bonding-enhancing effective amount(preferably between about 0.001% and about 20%, based upon the weight ofthe composition) of a surfactant selected from the group consisting ofpiperazine-substituted organosulfonates, piperazinone-substitutedorganosulfonates, and combinations thereof.

In still another aspect, the present invention relates to a method forcleaning a porous surface (such as asphalt or concrete) which comprisescontacting the porous surface with a cleaning-effective amount(preferably between about 0.001% and about 20%, based upon the weight ofthe composition) of a surfactant selected from the group consisting ofpiperazine-substituted organosulfonates, piperazinone-substitutedorganosulfonates, and combinations thereof.

These and other aspects will become apparent upon reading the followingdetailed description of the invention.

DETAILED DESCRIPTION OF THE INVENTION

It has now been surprisingly found in accordance with the presentinvention that the use of a surfactant selected from the groupconsisting of piperazine-substituted organosulfonates,piperazinone-substituted organosulfonates, and combinations thereof, inaccordance with the present invention enhances the cleaning efficacy ofhard surface cleaning compositions (such as metal and concrete cleaningcompositions), and also enhances the adhesion efficacy, onto poroussubstrates, of adhesive compositions into which this surfactant isincorporated. Without wishing to be bound by any particular theory, itis believed that this cleaning and adhesion-promoting efficacy isattributable, at least in part, to the low surface tension andinterfacial tension associated with these surfactants, which, in turn,imparts good wetting characteristics to the adhesive- orcleaning-composition containing the surfactant.

In another surprising aspect of the present invention, the use of theabove-described surfactant in a concrete-forming formulationadvantageously reduces the amount of voids in the subsequently-formedconcrete, thereby facilitating the production of denser, strongerconcrete. Conversely, the concrete forming formulation can be suitablyprocessed in a manner to provide a decreased density with uniformsmall-sized voids, if desired by the incorporation of a specificsurfactant such as that commercially available as POLY-TERGENT SL-62surfactant, if desired.

The piperazine-substituted and piperazinone-substituted organosulfonatesurfactant/wetting agents employed in the present invention have a lowinterfacial tension and a low critical micelle concentration ("CMC").These surfactants are suitable for use in a variety of applications,including, for example, in the cleaning of porous and hard surfaces,including, but not limited to, concrete, asphalt, masonry, porousceramic, wood and wood-like materials, composite woods such as ply-woodand compressed board, stone such as brownstone and redstone, plaster,combinations thereof, and the like. These surfactants are also useful asa concrete emulsion mix additive in order to disperse dyes or increaseor decrease the density of a concrete-forming composition, as discussedabove.

The piperazine-substituted organosulfonate useful in the presentinvention is suitably produced by reacting, for example, an aralkylether sulfonic acid with a piperazine compound. Likewise, thepiperazinone-substituted organosulfonate useful in the present inventionis suitably prepared by reacting an aralkyl ether sulfonic acid with apiperazinone compound. Particularly advantageous aralkyl ethersulfonates are those selected from the group consisting of alkylateddiphenyl oxide sulfonates having at least one alkyl-substitution on aphenyl ring and wherein said alkyl-substitution is selected from thegroup consisting of linear, branched, and cyclic alkyl substitutions,and combinations thereof. Although any piperazine compound can be used,preferred compounds include those selected from the group consisting of1,2-aminoethyl piperazine, 1,4-piperazinediethane sulfonic acid,anhydrous piperazine, hydrated piperazine, and combinations thereof.Illustrative piperazinone compounds are the 2-piperazinones, such as4-(2-aminoethyl)-2-piperazinone, 4-(2-hydroxyethyl)-2-piperazinone, andN,N-dimethyl-2-piperazinone, and combinations thereof.

Particularly advantageous for use in preparing thepiperazine-substituted organosulfonates and piperazinone-substitutedorganosulfonates useful in the present invention are the alkylateddiphenyl oxide sulfonate anionic surfactants corresponding to thefollowing formula or to a mixture of compounds corresponding to thefollowing formula: ##STR1## wherein each R is independently a saturatedalkyl or substituted saturated alkyl radical or an unsaturated alkyl orsubstituted unsaturated alkyl radical each m and n is independently 0, 1or 2; each M is independently hydrogen, an alkali metal, an alkalineearth metal, or ammonium or substituted ammonium; and each x and y areindividually 0 or 1. Preferably, each R group is independently an alkylgroup having from about 8 to about 24 carbon atoms, even more preferablyabout 10 to about 20 carbon atoms, and most preferably about 12 to about16 carbon atoms, with 16 carbon atoms being especially preferred. Thealkyl groups can be linear, branched or cyclic, with linear or branchedradicals being preferred. The M+ ammonium ion radicals are of theformula (R')₃ NH+ wherein each R' is independently hydrogen, a C₁ -C₄alkyl or a C₁ -C₄ hydroxyalkyl radical. Illustrative C₁ -C₄ alkyl orhydroxyalkyl radicals include methyl, ethyl, propyl, isopropyl, butyl,hydroxymethyl and hydroxyethyl. Typical ammonium ion radicals includeammonium (N+H₄), methylammonium (CH₃ N+H₃), ethylammonium (C₂ H₅ N+H₃) ,dimethylammonium ((CH₃)₂ N+ H₂), methylethylammonium (CH₃ N+H₂ C₂ H₅,trimethylammonium ((CH₃)₃ N+H) dimethylbutylammonium ((CH₃)₂ N+HC₄ H₉hydroxyethylammonium (HOCH₂ CH₂ N+H₃) and methylhydroxyethyl ammonium(CH₃ N+H₂ CH₂ CH₂ OH) . Preferably, each M is hydrogen, sodium, calcium,potassium or ammonium.

Alkylated diphenyl oxide sulfonates and their methods of preparation arewell-known and reference is made thereto for the purposes of thisinvention. Representative methods of preparation of sulfonates aredisclosed in U.S. Pat. Nos. 3,264,242; 3,634,272; and 3,945,437.Commercial methods of preparation of the alkylated diphenyl oxidesulfonates generally do not produce species which are exclusivelymonoalkylated, monosulfonated, dialkylated or disulfonated. Thecommercial available species are predominantly (greater than 90 percent)disulfonated and are a mixture of mono- and dialkylated with thepercentage of dialkylation being about 15 to about 25 and the percentageof monoalkylation being about 75 to 85 percent. Most typically, thecommercially available species are about 80 percent monoalkylated and 20percent dialkylated.

Two illustrative commercially available solutions containing alkylateddiphenyl oxide sulfonate surfactants are DOWFAX® 8390 and DOWFAX® 8390Asurfactants, trademarked products of The Dow Chemical Company. In each,the alkyl group R is predominantly a hexadecyl (C₁₆) group. DOWFAX®8390Atypically contains about 25 percent of the acid forms of the surfactant,that is, in which M is hydrogen. DOWFAX® 8390 surfactant typicallycontains about 35 percent of the sodium salts of the surfactant, thatis, in which M is sodium. DOWFAX® 8390A solution fully or partiallyneutralized with ammonium hydroxide is also suitable for use in thepresent invention.

The alkylated diphenyl oxide sulfonate compound is suitably reacted withthe piperazine compound to produce the desired piperazine salt using amolar ratio of sulfonate compound to piperazine compound of betweenabout 10:1 and about 1:10, preferably between about 2:1 and about 1:2.

The organic or inorganic salt of a polycarboxylated alcohol alkoxylateis preferably selected from the group consisting of organic or inorganicsalts of the following: polycarboxylated linear alcohol alkoxylates,polycarboxylated branched alcohol alkoxylates, polycarboxylated cyclicalcohol alkoxylates, and combinations thereof. Suitable polycarboxylatedalcohol alkoxylates are shown by the empirical structural formula:##STR2## wherein R is a hydrocarbon radical having between about 6 andabout 18 carbon atoms, R' is hydrogen or a hydrocarbon between 1 and 8carbon atoms, x and y are independently selected from the groupconsisting of hydrogen, methyl, and succinic acid radicals, with theproviso that at least one x or y per molecule is a succinic acidradical, and f is between 1 and 25. Preferred polycarboxylated alcoholalkoxylates are those having a backbone containing both poly(propyleneoxide) and poly(ethylene oxide) blocks, and such preferredpolycarboxylated alcohol alkoxylates are readily commercially available,for example, under the registered trademark POLY-TERGENT CS-1surfactant, a product of Olin Corporation. Any of a wide variety ofinorganic or organic bases can be utilized to neutralize at least aportion of the acid groups on the polycarboxylated alcohol alkoxylate toprovide the desired salt thereof, such as for example alkali metalhydroxides, alkaline earth metal hydroxides, and metal-free hydroxides,including potassium hydroxide, ammonium hydroxide, calcium hydroxide,magnesium hydroxide, ammonia, mono-, di- and tri-ethanol amines, andcombinations thereof. Sodium hydroxide is preferred, and althoughpotassium hydroxide can be employed, it is not preferred. The organic orinorganic base is preferably employed in at least an equimolar amountrelative to the number of moles of polycarboxylated alcohol alkoxylateused. The polycarboxylated alcohol may also contain a polycarboxylicacid, for example, polyacrylic acid, along with the starting alcoholalkoxylate and esters of the alkoxylate and the said polycarboxylicacid.

The alcohol alkoxylate employed in the present invention is suitablyselected from a wide range of such compounds, as disclosed, for example,in U.S. Pat. No. 3,956,401. Illustrative linear alcohol alkoxylates areshown by the formula: ##STR3## wherein R⁴ is a linear, alkyl hydrocarbonhaving, for example, an average of from about 7 to about 10 carbonatoms, R⁵ is a linear, alkyl hydrocarbon of about 1 to about 4 carbonatoms, R⁶ is a linear, alkyl hydrocarbon of about 1 to about 4 carbonatoms, d is an integer of about 1 to about 6, e is an integer of about 4to about 15, and f is an integer of about 4 to about 25.

Useful linear alcohol alkoxylates are commercially available, forexample, under the registered trademark POLY-TERGENT SL-42, a product ofOlin Corporation. If desired, the alcohol alkoxylate is suitablyend-capped with a lower alkyl group, and such a product is commerciallyavailable as POLYTERGENT SLF-18, a propylene oxide capped linear alcoholalkoxylate that is also a product of Olin Corporation, and theseend-capped linear alcohol alkoxylates have been found by the presentinventors to provide desirably low foaming during use. Also advantageousfor use in accordance with the present invention is a surfactant withinthe group commercially available as POLY-TERGENT SLF-18B seriessurfactants, which are surfactants characterized by enhancedbiodegradability and are also products of Olin Corporation, which arealkene oxide capped linear alcohol alkoxylates, containing ethyleneoxide moieties in the backbone, and suitably also containing at leastone propylene oxide moiety in the backbone, as disclosed, for example,in U.S. Pat. Nos. 4,925,587 and 4,898,621. Use of the POLY-TERGENTSLF-18 and/or POLY-TERGENT SLF-18B surfactants to comprise component (c)in accordance with the present invention has been by the presentinventors to avoid the need for an antifoaming agent in the concentratesand working compositions of the present invention.

Nonionic surfactants optionally employed in the compositions and methodsof the present invention include those commercially available, such as,for example, Tergitol XL-80N surfactant, a trademarked product of UnionCarbide Chemicals and Plastics Technology Corp., Danbury, Connecticut.Tergitol XL-80N is a mixture of C₈ -C₁₀ ethoxylated and propoxylatedprimary alcohols having an average molecular weight of approximately420. The mixture decomposes rather than boils upon heating, and has aflash point of 425° F. (Cleveland open cup ASTM D 92.218° C.) It has afreezing point of -3° C. a specific gravity of 0.98 at 20° C. and is acloudy liquid which is fully soluble in water.

Another useful nonionic surfactant is NEODOL® 91-6 surfactant, atrademarked surfactant product of Shell Chemical Company, Geismar, La.NEODOL® 91-6 surfactant is a detergent range mixture of C₉ -C₁₁ linearprimary alcohol ethoxylates having an average of 6 moles of ethyleneoxide per mole of alcohol. NEODOL® 91-6 is a slightly viscous liquidhaving a pour point of 45° F. and a melting point of 42°-48° F. Itssolubility in water is complete, although at high concentrations theproduct may form a gel with water. NEODOL® 91-6 surfactant contains lessthan 6 parts per million ethylene oxide. NEODOL® 91-6 surfactantpossesses a hydroxyl number of 126-140 milligrams potassium hydroxideper gram.

While these surfactants are suitable for use in the present invention,others within a wide range of molecular weights can also be successfullyemployed in aqueous or organic solvent solution. For example,surfactants with linear C₉ -C₁₁ carbon chains and five or six EO or POgroups are expected to provide desirable results.

An antifoaming agent (also referred to herein as a "defoaming agent" or"defoamer") is optionally employed in accordance with the process of thepresent invention. The degree of foaming encountered depends to a largeextent upon the specific compounds selected for components (a), (b) and(c), as well as upon the physical method employed for cleaning a surfaceor providing adhesion to a substrate, as desired. Illustrative defoamersinclude silicon oils, mineral oils, modified alcohol ethoxylate, EO/POblock copolymers, phosphate ester, hydrophobic silica, and Fattyalcohols as well as blends of these defoamers. The antifoaming agentshould be selected and employed at a concentration such that thedetergency of the surfactant(s) and the corrosion inhibition of the2-piperazinone are not unduly reduced. The antifoaming agent isdesirably employed in the formulation at a concentration of 0.01 to 2percent by weight, preferably at about 0.02 percent by weight. Otheruseful antifoaming agents include liquid silicone emulsions manufacturedand sold by Dow Corning Corporation (Midland, Mich.) under itstrademarks "DOW CORNING® X2-1410 ANTIFOAM" and "DOW CORNING® X2-2210ANTIFOAM".

The reaction conditions employed in fabricating the compositions andmethods of the present invention are not narrowly limited to anyparticular conditions. It is preferred to carry out the reaction stepsto form the compositions at a temperature of between about 25° C. andabout 150° C., although a higher or lower temperature is suitablyemployed if desired. Reaction pressure can be selected as desired.Typically, super- or sub-atmospheric reaction pressure is not necessaryfor the reactions employed in the processes of the present invention.Atmospheric pressure is preferred in order to avoid the expense ofspecial reaction vessels. However, elevated pressures can be used, ifdesired, and these superatmospheric pressures of up to 10 atmospheres orhigher are suitably utilized if desired.

The following examples are intended to illustrate, but in no way limitthe scope of, the present invention.

EXAMPLE 1 Concrete Cleaning Example

Part A--Preparation of Surfactant A

A premier Caframo (high intensity mixer) at torque of 500 to 1,000 rpmwas used to blend a premix of 40 grams of Poly-Tergent(R) 2A1 acid(Alkyl diphenylether disulfonate), 3.91 grams of water and 8.04 grams of1 (2, Aminoethyl)piperazine to neutralize 2A1 acid to a pH of 6, untilit was totally homogeneous. The blend is 77 percent active.

A premier Caframo (high intensity mixer) at torque of 500 to 2,000 rpmwas used to mix 7.136 grams of CS-1 acid (polycarboxylated linearalcohol alkoxylate) with 21,407 grams Poly-Tergent(R) SL 18 (linearalcohol alkoxylate) until it was in solution. 40 grams of above 77percent active component and 7.196 grams of defoamer were added to thismixture, and mixed until it was totally homogeneous. Followinghomogenizing, 2.106 grams of 50% NaOH were added to neutralize the CS-1acid and mixed for 20 minutes. The resulting surfactant product showedlow foaming at room temperature and at an elevated temperature of 120°F. This surfactant product is identified as Surfactant A in Examples 1-9hereof.

Part B--Preparation of Concrete Cleaning Formulation

A concrete cleaning formulation was prepared by mixing the followingcomponents:

    ______________________________________                                        Component:        Amount:                                                     ______________________________________                                        Diethanolamine        25     grams                                            NaOH (50%)            46     grams                                            Na2SiO3               26     grams                                            Potassium Carbonate   11     grams                                            Poly-Tergent @ SL-42* 1      grams                                            Ethylene Glycol       14     grams                                            Water                 877    grams                                            Surfactant A          7      grams                                            ______________________________________                                         *This substituted polycarboxylated alcohol is commercially available.    

Part C--Concrete/Asphalt Cleaning

The above cleaning formulation was evaluated for efficacy in cleaningasphalt and concrete. Cleaning properties measurements were made usingASTM D 4258 Test Method D425883 (Reapproved 1992) in order to measurethe surface cleaning of concrete by the cleaning formulation in removinggrease, dirt, and loose material prior to the application of coatings.Procedures employed in this test regimen include broom cleaning, vacuumcleaning, air blast cleaning, water cleaning, detergent water cleaning,and steam cleaning. This test regimen and the associated cleaningmethodology are not intended to alter the surface profile of theconcrete but to test the cleaning of the concrete surface.

The above-described concrete cleaning formulation was evaluated forcleaning efficacy using modified ASTM D 4258 Test Method D4258-83(Reapproved 1992). Briefly this modified test procedure involvesfollowing: 1) Prepare the cleaning solution according to the aboveformulation. 2) Pour 5 drop of above surfactant on the oil or greasesurface and wait 20 to 30 minute let it penetration and dry. 3) Cleaningthe surface with a stiff-bristle in order to remove heavy deposits ofgrease or oil. 4) Flush surface thoroughly with clean potable water andremoved all residues of the cleaning gent. 5) Repeat flushing until thepH of the water meets the acceptance criteria of Test Method D4262-83(Reapproved 1988) cleaning cycle. When tested in accordance with thisprotocol, the above-described cleaning formulation provided excellentconcrete cleaning results.

EXAMPLE 2-6 Additional Concrete Cleaning Examples

Following the procedure given in Example 1 above, additional cleaningformulations (identified as Examples 2 through 6 below) were preparedand tested using the test regimen described in Example 1. Each of theseformulations provided excellent concrete cleaning performance results inthose tests.

EXAMPLE 2 Concrete Cleaning Formulation

    ______________________________________                                        EDTA, (K salt) Dihydrate                                                                             30     grams                                           NaOH (50%)             10     grams                                           Na2SiO3 5H2O           60     grams                                           Poly-Tergent ® SL-42*                                                                            20     grams                                           Water                  873    grams                                           Surfactant A           7      grams                                           ______________________________________                                    

EXAMPLE 3 Concrete Cleaning Formulation

    ______________________________________                                        EDTA, (K salt) Dihydrate                                                                             30     grams                                           NaOH (50%)             10     grams                                           Na2SiO3 5H2O           60     grams                                           NONYL PHENOL           20     grams                                           Water                  873    grams                                           Surfactant A           7      grams                                           ______________________________________                                    

EXAMPLE 4 Concrete Cleaning Formulation

    ______________________________________                                        EDTA, (K salt) Dihydrate                                                                             30     grams                                           NaOH (50%)             10     grams                                           Na2SiO3.5H2O           60     grams                                           Surfactant A           20     grams                                           Water                  880    grams                                           ______________________________________                                    

EXAMPLE 5 Concrete Cleaning Formulation

    ______________________________________                                        Na2SiO3.5H2O            30     grams                                          Alcohol AlkoxylatePhosphateester                                                                      20     grams                                          Tridecyl Alcohol Ethoxylates                                                                          25     grams                                          Ethlene Glycol butyl ether                                                                            65     grams                                          Sodium tripolyphosphate 30     grams                                          Water                   830    grams                                          Surfactant A            7      grams                                          ______________________________________                                    

EXAMPLE 6 Dry Concrete Cleaning Formulation

    ______________________________________                                        Na2SiO3            20%                                                        Light soda ash     37%                                                        NAOH Beads         25%                                                        Sodium tripolyphosphate                                                                          15%                                                        Surfactant A        3%                                                        ______________________________________                                    

Note that the dry formulation of Example 6 was tested in the protocol ofExample 1 after prewetting the concrete test sample to be cleaned, andthen sprinkling the powderized dry cleaning formulation onto theconcrete.

EXAMPLE 7 Metal Cleaning--Light Duty Formulation

The following formulation was prepared and tested for cleaning hardenedgrease and/or oil from a metal surface on metal test panels.

    ______________________________________                                        Formulation        % by wt. of Component                                      ______________________________________                                        Na2SiO3 (Anhydrous)                                                                              3%                                                         Ethylene Glycol butyl ether                                                                      1%                                                         Tetrapotassium Pyrophosphate                                                                     3%                                                         Water              90%                                                        Surfactant A       3%                                                         ______________________________________                                    

Example 8 Metal Cleaning--Heavy Duty Formulation

The following formulation was prepared and tested for cleaning hardenedgrease and/or oil from a metal surface on metal test panels.

    ______________________________________                                        Dry Formulation   % by wt. of Component                                       ______________________________________                                        Na2SiO3           36%                                                         Soda ash          26%                                                         NAOH Beads        15%                                                         TetraSodium pyrophosphate                                                                       20%                                                         Surfactant A       3%                                                         ______________________________________                                    

The formulations of Examples 7 and 8 above were both found to beeffective in emulsifying grease and/or oil on the metal test panels,thereby rendering the grease and/or oil easy to remove from the testpanels.

EXAMPLE 9 Hard Surface Cleaning (Tile)

Part A--TEST PROCEDURE: A modified version of the CSMA's newly approvedMethod for Applying and Measuring the Removal of Lime Soap was used todetermine detergency, and the procedure used was as follows: Amulti-component soil consisting of bar soap, shampoo, clay, body oils,and hardness ions was prepared, dried and pulverized. The parent soilwas suspended in a diluent and sprayed onto standard black ceramic tilesusing an air brush. The soil was heated onto the tiles to make ittenacious. A wet sponge sprayed with a cleaning formulation and aGardner Abrasion Tester were used to simulate soil removal. Detergencywas calculated from spectrocolorimeter readings.

A few changes were made to this procedure for better differentiation andreproducibility:

1) 0.20-0.25 grams of soil were applied per tile instead of 0.10-0.15grams.

2) The soil was heated on the tile for four minutes rather than twominutes.

3) Approximately 0.5 grams of test product was sprayed onto the spongerather than directly onto the soiled area of the tile.

The rest of the procedure was followed as written.

    ______________________________________                                        % Area Cleaned                                                                           % Surfactant Used                                                                              Surf. Type                                        ______________________________________                                        37.526      4%              Surfactant A                                      24.1457     4%              Surfactant A                                      52.3813     1%              Surfactant A                                      53.2372     1%              Surfactant A                                      3.8634     100%             WATER only                                        -16.5575   100%             WATER only                                        0.9835     100%             WATER only                                        23.1374    100%             Comparison 1                                      21.08438   100%             Comparison 1                                      30.18845   100%             Comparison 2                                      34.44544   100%             Comparison 2                                      54.18409   100%             Comparison 3                                      34.65991   100%             Comparison 3                                      ______________________________________                                        Comparison 1 Formulation                                                      ______________________________________                                        Poly-Tergent ® CS-1 5%                                                    Poly-Tergent ® SL-62                                                                              10%                                                   Preservative, Dye, Fragrance                                                                          QS*                                                   Water                   to 100%                                               ______________________________________                                        Comparison 2 Formulation                                                      ______________________________________                                        Poly-Tergent ® CS-1 5%                                                    Poly-Tergent ® SL-62                                                                              12.5%                                                 Preservative, Dye, Fragrance                                                                          QS*                                                   Water                   to 100%                                               ______________________________________                                        Comparison 3 Formulation                                                      ______________________________________                                        Isopropyl Alcohol       12%                                                   Poly-Solv ® DPM     4%                                                    Poly-Tergent ® 3B2  .15%                                                  Poly-Tergent ® CS-1 .15%                                                  Acetic Acid             to pH 4.5                                             Preservative, Dye, Fragrance                                                                          QS*                                                   Water                   to 100%                                               ______________________________________                                    

The above results show that Surfactant A provides excellent cleaningefficacy in cleaning tile, as compared to water or the comparisonconventional surfactants identified above as Comparisons 1-3.

While the invention has been described above with reference to specificembodiments thereof, it is apparent that many changes, modifications andvariations can be made without departing from the inventive conceptdisclosed herein. Accordingly, it is intended to embrace all suchchanges, modifications and variations that fall within the spirit andbroad scope of the appended claims.

What is claimed is:
 1. A concrete-forming composition comprising:(a) abase component consisting of a combination of cement and silica, (b)water, as a carrier, and (c) a wetting agent, in an amount of betweenabout 0.01% and about 25% by weight based upon the weight of thecomposition, selected from the group consisting ofpiperazine-substituted organosulfonates, piperazinone-substitutedorganosulfonates, and combinations thereof.
 2. The composition of claim1 wherein said piperazine-substituted organosulfonate is produced byreacting an aralkyl ether sulfonic acid with a piperazine compoundselected from the group consisting of 1,2-aminoethyl piperazine,1,4piperazinediethane sulfonic acid, anhydrous piperazine, hydratedpiperazine, and combinations thereof.
 3. The composition of claim 2wherein said aralkyl ether sulfonic acid is selected from the groupconsisting of alkylated diphenyl oxide sulfonic acid having at least onealkyl-substitution on a phenyl ring and wherein said alkyl-substitutionis selected from the group consisting of linear, branched, and cyclicalkyl substitutions, and combinations thereof.
 4. The composition ofclaim 1 which additionally contains a polycarboxylated alcoholalkoxylate selected from the group consisting of polycarboxylated linearalcohol alkoxylates, polycarboxylated branched alcohol alkoxylates,polycarboxylated cyclic alcohol alkoxylates, and combinations thereof.5. In a concrete-forming composition comprising water, silica andcement, the improvement comprising said composition additionallycontaining a concrete emulsion mix additive selected from the groupconsisting of piperazine-substituted organosulfonates,piperazinone-substituted organosulfonates, and combinations thereof.